Salts of nitroform with hydrazines



i or. explosive. component. nitroform is severely curtailed because it is highly acidic and has a low decomposition point, about 30 C. Ni-

1-methyll-phenylhydrazine;

3,297,747 Patented Jan. 10, 1967 3,297,747 SALTS on NITROFORM WITH HYDRAZINES James Rm Thornton, Tamaqua, Pan, assignor to Atlas Chemical Industries, Inc., Wilmington, Del., a corporation of" Delaware No Drawing. Filed Dec. 26, 1963, Ser. No. 333,662

3 Claims. ((31.260-501) Theupresent invention relates to salts of nitroform and "more specifically, to salts of nitroform with hydrazine and substituted hydrazines. Further the present invention relates to a method of producing such salts.

Nitroform, .trinitromethane, having a plurality of nitro groups. with a single carbon and a single hydrogen atom would at first glance be thought to be a useful explosive However, the usefulness of troformgwhas a very penetrating and unpleasant odor. Although 11 it appears attractive on paper, the physical disadvantages of nitroform have substantially eliminated it from use in. the explosives or propellant art. Mixtures of nitroform with other materials, such as amines odor. and exhibit inhibited acidity. The present salts are highly ginflammable but do not appear to be deton atablel. under ordinary circumstances. The salts are useful to sensitize ammonium nitrate and may aptly be used ini propellant compositions and systems.

In accord withthe present invention, a nitroform salt isi provided which consists of nitroform and a member of the group. consisting of hydrazine, monoalkyl hydrazines, such as methylhydrazine, and ethylhydrazine; monoarylhydrazines, such as 2,4'dinitrophenylhydrazine, phenylhydrazine, 2,5-dichlorophenylhydrazine, l-naphthylhydrazine, p-nitrophenylhydrazine, p-bromophenylhydrazine, 2,4,6-trinitrophenylhydrazine, and 2,4,6-trichlorophenylhydrazineg alkylaryl hydrazines, such as,

unsymmetrical dialkylhydra'zines, such as 1,1-dimethylhyclrazine, and; unsymmetricalidiarylhydrazines, such as 1,1-diphenylhydrazine,

and .1-benzyl-1-phenylhydrazine.

Thesalts ofthe present invention may be prepared by initially dissolving the nitroform component in a short chain alcohol and then slowly adding hydrazine or a hydrazine. derivative to precipitate the nitroform salt. Al-

cohols containing from 2 to 6 carbon atoms are particularlyi adapted to use in the present invention, for exampleQuethyl, methyl, propyl, isopropyl, and butyl alcohols. The nitroform-hydrazine salt or the nitroformhydrazine .derivative salt product may be recovered by U separatingit from the supernatant alcohol by filtration. If dCSiIGdi the product maybe recrystallized from a short chain alcohol solution. The salt products of the present invention are substantially odorless and are stable over 1 a long period of time, generally over. a period of 6 months and at temperatures ranging from 18 to 100 C.

3 .The following examples are illustrative of the processtoftproducing the present nitroform salts:

Example 1 151 grams of nitroform (1 mole) was dissolved in 1000 cc. of iso-propylalcohol. Hydrazine was then added to the solution in a dropwise manner. A precipitate formed. Additional hydrazine was added until precipitation was complete. The precipitate was separated by filtration and dried. The dried product was then recrystallized from a matrix of iso-propyl alcohol. 91 grams of product, nitroform-hydrazine salt, was recovered representing Example 2 Nitroform and 2,4-dinitrophenylhydrazine was reacted by the method of Example 1. The melting range of the product was found to be 120 C. to 123 C. The total nitrogen content was found to be 23.17% by weight of the product. The calculated nitrogen content for the nitroform-2,4-dinitrophenylhydrazine salt product was 28.09%. Again the salt product was found to be quite odorless and stable over a period of 18 months at temperatures ranging from 18 to C.

Other salts of substituted hydrazines and nitroform may be prepared in a manner similar to the method described in Example 2, for example, nitroform may be reacted with any of the following: l-methyl-l-phenylhydrazine, 1,1-dimethylhydrazine and 1,1-diphenylhydrazine, to produce nitroform salts.

What is claimed is:

1. A salt of nitroform and a member of the group consisting of hydrazine, 2,4-dinitrophenylhydrazine, phenylhydrazine, p-bromophenylhydrazine, l-methyl-lphenylhydrazine, p-nitrophenylhydrazine, 1,1-diphenylhydrazine, l-benzyl-l-phenylhydrazine, l-naphthylhydrazine, methylhydrazine, ethylhydrazine, 2,5-dichlorophenylhydrazine, 2,4,6-trichlorophenylhydrazine, 1,1-dimethylhydrazine, 2,4,6-trinitrophenylhydrazine.

2. A salt of nitroform and hydrazine.

3. A salt of nitroform and 2,4-dinitropheny1hydrazine.

References Cited by the Examiner UNITED STATES PATENTS 2,961,467 11/1960 Darr 260-583 2,963,507 12/ 1960 Ruduer 260501 2,992,910 7/1961 Wetterholm 260644 XR OTHER REFERENCES Organischen CHARLES B. PARKER, Primary Examiner. R. V. HINES, Assistant Examiner. 

1. A SALT OF NITROFORM AND A MEMBER OF THE GROUP CONSISTING OF HYDRAZINE, 2,4-DINITROPHENYLHYDRAZINE, PHENYLHYDRAZINE, P-BROMOPHENYLHYDRAZINE, 1-METHYL-1PHENYLHYDRAZINE, P-NITROPHENYLHYDRAZINE, 1,1-DIPHENYLHYDRAZINE, 1-BENZYL-1-PHENYLHYDRAZINE, 1-NAPHTHYLHYDRAZINE, METHYLHYDRAZINE, ETHYLHYDRAZINE, 2,5-DICHLOROPHENYLHYDRAZINE, 2,4,6-TRICHLOROPHENYLHYDRAZINE, 1,1-DIMETHYLHYDRAZINE, 2,4,6-TRINITROPHENYLHYDRAZINE. 